Process for making a partially coated electrode active material, and electrode active material

ABSTRACT

A process for making a partially coated electrode active material may involve: (a) providing an electrode active material of the formula Li1+xTM1−xO2, wherein TM is a combination of Ni, Co and, optionally, Mn, and, optionally, at least one metal selected from Al, Ti, Mo, W, and Zr, and x is in the range of from zero to 0.2, wherein at least 60 mole-% of the transition metal of TM is Ni, and wherein the electrode active material has a residual moisture content in the range of from 50 to 1,000 ppm; (b) treating the electrode active material with a metal alkoxide or metal halide or metal amide or alkyl metal compound; (c) treating the material obtained in (b) with moisture; and (d) repeating the sequence of (b) and (c) twice to 4 times, wherein, in the last sequence of (b) and (c), moisture is at least partially substituted by ozone.

The present invention is directed towards a process for making a partially coated electrode active material wherein said process comprises the following steps:

-   (a) Providing an electrode active material according to general     formula Li_(1+x)TM_(1−x)O₂, wherein TM is a combination of Ni, Co     and, optionally, Mn, and, optionally, at least one metal selected     from Al, Ti, Mo, W, and Zr, and x is in the range of from zero to     0.2, wherein at least 60 mole-% of the transition metal of TM is Ni,     and wherein said electrode active material has a residual moisture     content in the range of from 50 to 1,000 ppm, -   (b) treating said electrode active material with a metal alkoxide or     metal halide or metal amide or alkyl metal compound, -   (c) treating the material obtained in step (b) with moisture, -   (d) repeating the sequence of steps (b) and (c) twice to 4 times,     wherein in the last sequence of steps (b) and (c), moisture is at     least partially substituted by ozone.

Lithium ion secondary batteries are modern devices for storing energy. Many application fields have been and are contemplated, from small devices such as mobile phones and laptop computers through car batteries and other batteries for e-mobility. Various components of the batteries have a decisive role with respect to the performance of the battery such as the electrolyte, the electrode materials, and the separator. Particular attention has been paid to the cathode materials. Several materials have been suggested, such as lithium iron phosphates, lithium cobalt oxides, and lithium nickel cobalt manganese oxides. Although extensive research has been performed the solutions found so far still leave room for improvement.

One problem of lithium ion batteries is attributed to undesired reactions on the surface of the cathode active materials. Such reactions may be a decomposition of the electrolyte or the solvent or both. It has thus been tried to protect the surface without hindering the lithium exchange during charging and discharging. Examples are attempts to coat the cathode active materials with, e.g., aluminium oxide or calcium oxide, see, e.g., U.S. Pat. No. 8,993,051.

The efficiency of the process, however, may still be improved. Especially in embodiments wherein the particles have a tendency to agglomerate the efficiency sometimes leaves room for improvement both in respect to reaction time and percentage of covered particles.

It was therefore an objective of the present invention to provide a process by which electrode active materials may be coated to reduce the tendency of resistance build-up during repeated cycling.

Accordingly, the process as defined at the outset has been found, hereinafter also referred to as inventive process or as process according to the (present) invention. The inventive process is a process for making a coated electrode active material.

The term “partially coated” as used in the context with the present invention refers to at least 80% of the particles of a batch of particulate material being coated, and to at least 50% of the surface of each particle being coated, for example 75 to 99.99% and preferably 80 to 90%.

The thickness of such coating may be very low, for example 0.1 to 5 nm. In other embodiments, the thickness may be in the range of from 6 to 15 nm. In further embodiments, the thickness of such coating is in the range of from 16 to 50 nm. The thickness in this context refers to an average thickness determined mathematically by calculating the amount of metal alkoxide or metal halide or metal amide or alkyl metal, respectively, per particle surface in m² and assuming a 100% conversion.

Without wishing to be bound by any theory, it is believed that non-coated parts of particles do not react due to specific chemical properties of the particles, for example density of chemically reactive groups such as, but not limited to hydroxyl groups, oxide moieties with chemical constraint, or to adsorbed water.

In one embodiment of the present invention the electrode active material has an average particle diameter (D50) in the range of from 3 to 20 μm, preferably from 5 to 16 μm. The average particle diameter can be determined, e.g., by light scattering or LASER diffraction or electroacoustic spectroscopy. The particles are usually composed of agglomerates from primary particles, and the above particle diameter refers to the secondary particle diameter.

In one embodiment of the present invention, the electrode active material has a specific surface (BET), hereinafter also referred to as “BET surface”, in the range of from 0.1 to 1.5 m²/g. The BET surface may be determined by nitrogen adsorption after outgassing of the sample at 200° C. for 30 minutes or more and beyond this accordance with DIN ISO 9277:2010.

The inventive process comprises three steps (a), (b) and (c), in the context of the present invention also referred to as step (a), step (b) and step (c).

Step (a) includes providing an electrode active material according to general formula Li_(1+x)TM_(1−x)O₂, wherein TM is a combination of Ni, Co and, optionally, Mn, and, optionally, at least one metal selected from Al, Ti, Mo, W, and Zr, and x is in the range of from zero to 0.2, wherein at least 60 mole-% of the transition metal of TM is Ni, and wherein said electrode active material has a residual moisture content in the range of from 50 to 1,000 ppm.

TM may be selected from combinations of Mn and Ni, or Ni and Co, or from combinations of Ni, Mn and Co, optionally in each case with at least one more metal selected from Al, Ti, Zr, W, and Mo, preferably at least one of Al, W, Ti and Zr. Preferred are combinations of Ni and Co and of Ni and Co and Mn, optionally in each case with at least one more metal selected from Al, W, Ti and Zr.

In a preferred embodiment, TM is a combination of metals according to general formula (I)

(Ni_(a)Co_(b)Mn_(c))_(1-d)M_(d)  (I)

-   with -   a being in the range of from 0.6 to 0.95, -   b being in the range of from 0.025 to 0.2, -   c being in the range of from 0.025 to 0.2, and -   d being in the range of from zero to 0.1, -   M is Al, and

a+b+c=1.

Particularly preferred are Li_((1+x))[Ni_(0.6)Co_(0.2)Mn_(0.2)]_((1−x))O₂, Li_((1+x))[Ni_(0.7)Co_(0.2)Mn_(0.1)]_((1−x))O₂, and Li_((1+x))[Ni_(0.8)Co_(0.1)Mn_(0.1)]_((1−x))O₂, each with x as defined above.

Said electrode active material is preferably provided without any additive such as conductive carbon or binder but as free-flowing powder.

Said cathode active material provided in step (a) has a residual moisture content in the range of from 50 to 1,000 ppm, preferably from 100 to 400 ppm. The residual moisture content may be determined by Karl-Fischer titration.

In step (b), said electrode active material is treated with a metal alkoxide or metal halide or metal amide or alkyl metal compound.

In one embodiment of the inventive process, step (b) is performed at a temperature in the range of from 15 to 1000° C., preferably 15 to 500° C., more preferably 20 to 350° C., and even more preferably 50 to 150° C. It is preferred to select a temperature in step (b) at which metal alkoxide or metal amide or alkyl metal compound, as the case may be, is in the gas phase.

In one embodiment of the present invention, step (b) is carried out at normal pressure but step (b) may as well be carried out at reduced or elevated pressure. For example, step (b) may be carried out at a pressure in the range of from 5 mbar to 1 bar above normal pressure, preferably 10 to 150 mbar above normal pressure. In the context of the present invention, normal pressure is ambient pressure, for example 1 atm or 1013 mbar at sea level. In different altitudes, ambient pressure may be lower. In other embodiments, step (b) may be carried out at a pressure in the range of from 150 mbar to 560 mbar above normal pressure.

In a preferred embodiment of the present invention, alkyl metal compound or metal alkoxide or metal amide, respectively, is selected from Al(R¹)₃, Al(R¹)₂OH, AlR¹(OH)₂, M¹(R¹)_(4−y)H_(y), Al(OR²)₃, M¹(OR²)₄, M¹[NR²)₂]₄, and methyl alumoxane, wherein

R¹ are different or equal and selected from C₁-C₈-alkyl, straight-chain or branched,

R² are different or equal and selected from C₁-C₄-alkyl, straight-chain or branched,

M¹ is Ti or Zr, with Ti being preferred,

Metal alkoxides may be selected from C₁-C₄-alkoxides of aluminum, and transition metals. Preferred transition metals are titanium and zirconium. Examples of alkoxides are methanolates, hereinafter also referred to as methoxides, ethanolates, hereinafter also referred to as ethoxides, propanolates, hereinafter also referred to as propoxides, and butanolates, hereinafter also referred to as butoxides. Specific examples of propoxides are n-propoxides and iso-propoxides. Specific examples of butoxides are n-butoxides, iso-butoxides, sec.-butoxides and tert.butoxides. Combinations of alkoxides are feasible as well.

Preferred examples of metal C₁-C₄-alkoxides are Ti[OCH(CH₃)₂]₄, Ti(OC₄H₉)₄, Zn(OC₃H₇)₂, Zr(OC₄H₉)₄, Zr(OC₂H₅)₄, Al(OCH₃)₃, Al(OC₂H₅)₃, Al(O-n-C₃H₇)₃, Al(O-iso-C₃H₇)₃, Al(O-sec.C₄H₉)₃, and Al(OC₂H₅)(O-sec.-C₄H₉)₂.

Examples of aluminum alkyl compounds are trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, and methyl alumoxane.

Metal amides are sometimes also referred to as metal imides. An example of metal amides is Ti[N(CH₃)₂]₄.

Particularly preferred compounds are selected from metal C₁-C₄-alkoxides and metal alkyl compounds, and even more preferred is trimethyl aluminum.

In one embodiment of the present invention, the amount of metal alkoxide or metal amide or alkyl metal compound is in the range of 0.1 to 1 g/kg electrode active material.

Preferably, the amount of metal alkoxide or metal amide or alkyl metal compound, respectively, is calculated to amount to 80 to 200% of a monomolecular layer on the electrode active material per cycle.

In one embodiment of the present invention, step (b) is performed in a rotary kiln, in a free fall mixer, in a continuous vibrating bed or a fluidized bed. Step (b) of the inventive process as well as step (c)—that will be discussed in more detail below—may be carried out in the same or in different vessels.

In a preferred embodiment of the present invention, the duration of step (b) is in the range of from 1 second to 2 hours, preferably 1 second up to 10 minutes.

In a third step, in the context of the present invention also referred to as step (c), the material obtained in step (b) is treated with moisture.

In one embodiment of the present invention, step (c) is carried out at a temperature in the range of from 50 to 250° C.

In one embodiment of the present invention, step (c) is performed in a rotary kiln, in a free fall mixer, in a continuous vibrating bed or a fluidized bed.

In one embodiment of the present invention, step (c) is carried out at normal pressure but step (c) may as well be carried out at reduced or elevated pressure. For example, step (c) may be carried out at a pressure in the range of from 5 mbar to 1 bar above normal pressure, preferably 10 to 250 mbar above normal pressure. In the context of the present invention, normal pressure is 1 atm or 1013 mbar. In other embodiments, step (c) may be carried out at a pressure in the range of from 150 mbar to 560 mbar above normal pressure.

Steps (b) and (c) may be carried out at the same pressure or at different pressures, preferred is at the same pressure.

Said moisture may be introduced, e.g., by treating the material obtained in accordance with step (b) with moisture saturated inert gas, for example with moisture saturated nitrogen or moisture saturated noble gas, for example argon. Saturation may refer to normal conditions or to the reaction conditions in step (c).

In a preferred embodiment of the present invention, the duration of step (c) is in the range of from 1 second to 2 hours, preferably 1 second up to 10 minutes.

In one embodiment of the present invention, the reactor in which the inventive process is carried out is flushed or purged with an inert gas between steps (b) and (c), for example with dry nitrogen or with dry argon. Suitable flushing—or purging—times are 1 second to 30 minutes, preferably 1 second to 10 minutes. It is preferred that the amount of inert gas is sufficient to exchange the contents of the reactor of from one to 15 times. By such flushing or purging, the production of by-products such as separate particles of reaction product of metal alkoxide or metal amide or alkyl metal compound, respectively, with water can be avoided. In the case of the couple trimethyl aluminum and water, such by-products are methane and alumina or trimethyl aluminum that is not deposited on the particulate material, the latter being an undesired by-product. Said flushing may also take place after step (c), thus before another step (b). In this context, “dry” refers to a water content of less than 10 ppm by weight, for example 3 to 5 ppm.

In one embodiment of the present invention, each flushing step between (b) and (c) has a duration in the range of from one second to ten minutes.

In one embodiment of the present invention, the reactor is evacuated between steps (b) and (c). Said evacuating may also take place after step (c), thus before another step (b). Evacuation in this context includes any pressure reduction, for example 10 to 1,000 mbar (abs), preferably 10 to 500 mbar (abs).

Each of steps (b) and (c) may be carried out in a fixed bed reactor, in a fluidized bed reactor, in a forced flow reactor or in a mixer, for example in a compulsory mixer or in a free-fall mixer. Examples of fluidized bed reactors are spouted bed reactors. Examples of compulsory mixers are ploughshare mixers, paddle mixers and shovel mixers. Preferred are ploughshare mixers. Preferred ploughshare mixers are installed horizontally, the term horizontal referring to the axis around which the mixing element rotates. Preferably, the inventive process is carried out in a shovel mixing tool, in a paddle mixing tool, in a Becker blade mixing tool and, most preferably, in a ploughshare mixer in accordance with the hurling and whirling principle. Free fall mixers are using the gravitational force to achieve mixing. In a preferred embodiment, steps (b) and (c) of the inventive process are carried out in a drum or pipe-shaped vessel that rotates around its horizontal axis. In a more preferred embodiment, steps (b) and (c) of the inventive process are carried out in a rotating vessel that has baffles.

In one embodiment of the present invention, the rotating vessel has in the range of from 2 to 100 baffles, preferably 2 to 20 baffles. Such baffles are preferably flush mount with respect to the vessel wall.

In one embodiment of the present invention, such baffles are axially symmetrically arranged along the rotating vessel, drum, or pipe. The angle with the wall of said rotating vessel is in the range of from 5 to 45°, preferably 10 to 20°. By such arrangement, they can transport coated cathode active material very efficiently through the rotating vessel.

In one embodiment of the present invention, said baffles reach in the range of from 10 to 30% into the rotating vessel, referring to the diameter.

In one embodiment of the present invention, said baffles cover in the range of from 10 to 100%, preferably 30 to 80% of the entire length of the rotating vessel. In this context, the term length is parallel to the axis of rotation.

In a preferred embodiment of the present invention the inventive process comprises the step of removing the coated material from the vessel or vessels, respectively, by pneumatic conveying, e.g. 20 to 100 m/s.

In one embodiment of the present invention, the exhaust gasses are treated with water at a pressure above one bar and even more preferably higher than in the reactor in which steps (b) and (c) are performed, for example in the range of from 1.010 to 2.1 bar, preferably in the range of from 1.005 to 1.150 bar. The elevated pressure is advantageous to compensate for the pressure loss in the exhaust lines.

Step (d) includes repeating the sequence of steps (b) and (c) twice to 4 times, wherein in the last sequence of steps (b) and (c), moisture is at least partially substituted by ozone. Said latter step is hereinafter also referred to as step (c*).

Repetition may include repeating a sequence of steps (b) and (c) each time under exactly the same conditions or under modified conditions but still within the range of the above definitions. For example, each step (b) may be performed under exactly the same conditions, or, e.g., each step (b) may be performed under different temperature conditions or with a different duration, for example 120° C., then 10° C. and 160° C. each from 1 second to 1 hour.

In step (c*), ozone replaces moisture at least partially. It is preferred that in step (c*) no humidity is applied, and moisture is fully replaced by ozone. Ozone may be generated from oxygen under conditions known per se, and therefore, in step (c*) ozone usually is applied in the presence of oxygen.

During the application of ozone in step (c*) it is preferred that no nitrogen is present.

In one embodiment of the present invention, step (c*) is performed at normal pressure. In another embodiment of the present invention, step (c*) is performed at a pressure of 5 mbar to 1 bar above normal pressure, preferably 10 to 250 mbar above normal pressure. In another embodiment, step (c*) is performed at a pressure below normal pressure, for example at 100 to 900 mbar, preferably at 100 to 500 mbar below normal pressure. Step (c*) may be performed at temperatures from 20 to 300° C., preferred is from 100 to 300° C. and more preferred 150 to 250° C.

In one embodiment of the present invention, the duration of step (c*) is in the range of from 1 second to 2 hours, preferably from 1 second up to 10 minutes.

Step (c*) may be performed in the same type of vessel as step (c). Preferably, steps (c) and (c*) are performed in the same vessel.

A particulate electrode active material is obtained.

In one embodiment of the present invention, the sequence of step (b) and step (c*) is performed only once. In another embodiment, the sequence of step (b) and step (c*) is performed two to five times.

In one embodiment of the present invention, after step (c*) a post-treatment is performed, for example a thermal post-treatment (e). Such thermal post-treatment (e) may be performed by treating the particulate electrode active material obtained after step (c*) at a temperature in the range of from 150 to 800° C., preferably from 150 to 400° C., for example over a period of time in the range of from preferably from 180 to 350° C., for example over a period of 10 minutes to 2 hours.

A further aspect of the present invention is directed towards a particulate electrode active material, hereinafter also referred to as inventive electrode active material. Inventive electrode material has the general formula Li_(1+x)TM_(1−x)O₂, wherein TM is a combination of Ni, Co and, optionally, Mn, and, optionally, at least one metal selected from Al, Ti, Mo, W and Zr, and x is in the range of from zero to 0.2, wherein at least 60 mole-% of the transition metal of TM is Ni, and the outer surface of said particles is non-homogeneously coated with an acidic oxide selected from acidic aluminum oxyhydroxide, acidic alumina, acidic titania and acidic zirconia. Preferred is acidic aluminum oxyhydroxide and acidic alumina.

The non-homogeneous coating may be mapped by X-Ray Photoelectron Spectroscopy (“XPS”) or Transmission Electron Microscopy with Energy Dispersive X-ray Spectroscopy (“TEM-EDX”).

TM has been defined above.

In one embodiment of the present invention inventive electrode active material has an average particle diameter (D50) in the range of from 3 to 20 μm, preferably from 5 to 16 μm. The average particle diameter can be determined, e.g., by light scattering or LASER diffraction or electroacoustic spectroscopy. The particles are usually composed of agglomerates from primary particles, and the above particle diameter refers to the secondary particle diameter.

In one embodiment of the present invention, inventive electrode active material has a specific surface, hereinafter “BET surface”, in the range of from 0.1 to 1.5 m²/g. The BET surface may be determined by nitrogen adsorption after outgassing of the sample at 200° C. for 30 minutes or more and beyond this accordance with DIN ISO 9277:2010.

Preferably, TM in inventive particulate material is selected from Ni_(0.6)Co_(0.2)Mn_(0.2), Ni_(0.7)Co_(0.2)Mn_(0.1) and Ni_(0.8)Co_(0.1)Mn_(0.1) and said acidic oxide is selected from acidic aluminum oxyhydroxide and acidic alumina.

In one embodiment of the present invention inventive electrode active material has an average particle diameter (D50) in the range of from 3 to 20 μm, preferably from 5 to 16 μm. The average particle diameter can be determined, e.g., by light scattering or LASER diffraction or electroacoustic spectroscopy. The particles are usually composed of agglomerates from primary particles, and the above particle diameter refers to the secondary particle diameter.

In one embodiment of the present invention, the non-homogeneous coating has an average thickness in the range of from 0.2 to 2 nm, preferably 0.3 to 0.8 nm.

Inventive electrode active materials are very well suited for cathodes in lithium ion batteries. They exhibit a low resistance build-up in the cause of repeated cycling, for example 500 or more cycles.

A further aspect of the present invention refers to electrodes comprising at least one electrode material active according to the present invention. They are particularly useful for lithium ion batteries. Lithium ion batteries comprising at least one electrode according to the present invention exhibit a good discharge behavior. Electrodes comprising at least one electrode active material according to the present invention are hereinafter also referred to as inventive cathodes or cathodes according to the present invention.

Cathodes according to the present invention can comprise further components. They can comprise a current collector, such as, but not limited to, an aluminum foil. They can further comprise conductive carbon and a binder.

Suitable binders are preferably selected from organic (co)polymers. Suitable (co)polymers, i.e. homopolymers or copolymers, can be selected, for example, from (co)polymers obtainable by anionic, catalytic or free-radical (co)polymerization, especially from polyethylene, polyacrylonitrile, polybutadiene, polystyrene, and copolymers of at least two comonomers selected from ethylene, propylene, styrene, (meth)acrylonitrile and 1,3-butadiene. Polypropylene is also suitable. Polyisoprene and polyacrylates are additionally suitable. Particular preference is given to polyacrylonitrile.

In the context of the present invention, polyacrylonitrile is understood to mean not only polyacrylonitrile homopolymers but also copolymers of acrylonitrile with 1,3-butadiene or styrene. Preference is given to polyacrylonitrile homopolymers.

In the context of the present invention, polyethylene is not only understood to mean homopolyethylene, but also copolymers of ethylene which comprise at least 50 mol % of copolymerized ethylene and up to 50 mol % of at least one further comonomer, for example α-olefins such as propylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, and also isobutene, vinylaromatics, for example styrene, and also (meth)acrylic acid, vinyl acetate, vinyl propionate, C₁-C₁₀-alkyl esters of (meth)acrylic acid, especially methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and also maleic acid, maleic anhydride and itaconic anhydride. Polyethylene may be HDPE or LDPE.

In the context of the present invention, polypropylene is not only understood to mean homopolypropylene, but also copolymers of propylene which comprise at least 50 mol % of copolymerized propylene and up to 50 mol % of at least one further comonomer, for example ethylene and α-olefins such as butylene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-pentene. Polypropylene is preferably isotactic or essentially isotactic polypropylene.

In the context of the present invention, polystyrene is not only understood to mean homopolymers of styrene, but also copolymers with acrylonitrile, 1,3-butadiene, (meth)acrylic acid, C₁-C₁₀-alkyl esters of (meth)acrylic acid, divinylbenzene, especially 1,3-divinylbenzene, 1,2-diphenylethylene and α-methylstyrene.

Another preferred binder is polybutadiene.

Other suitable binders are selected from polyethylene oxide (PEO), cellulose, carboxymethylcellulose, polyimides and polyvinyl alcohol.

In one embodiment of the present invention, binder is selected from those (co)polymers which have an average molecular weight M_(w) in the range from 50,000 to 1,000,000 g/mol, preferably to 500,000 g/mol.

Binder may be cross-linked or non-cross-linked (co)polymers.

In a particularly preferred embodiment of the present invention, binder is selected from halogenated (co)polymers, especially from fluorinated (co)polymers. Halogenated or fluorinated (co)polymers are understood to mean those (co)polymers which comprise at least one (co)polymerized (co)monomer which has at least one halogen atom or at least one fluorine atom per molecule, more preferably at least two halogen atoms or at least two fluorine atoms per molecule. Examples are polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyvinylidene fluoride (PVdF), tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers and ethylene-chlorofluoroethylene copolymers.

Suitable binders are especially polyvinyl alcohol and halogenated (co)polymers, for example polyvinyl chloride or polyvinylidene chloride, especially fluorinated (co)polymers such as polyvinyl fluoride and especially polyvinylidene fluoride and polytetrafluoroethylene.

Inventive cathodes may comprise 1 to 15% by weight of binder(s), referring to electrode active material. In other embodiments, inventive cathodes may comprise 0.1 up to less than 1% by weight of binder(s).

A further aspect of the present invention is a battery, containing at least one cathode comprising inventive electrode active material, carbon, and binder, at least one anode, and at least one electrolyte.

Embodiments of inventive cathodes have been described above in detail.

Said anode may contain at least one anode active material, such as carbon (graphite), TiO₂, lithium titanium oxide, silicon, lithium or tin. Said anode may additionally contain a current collector, for example a metal foil such as a copper foil.

Said electrolyte may comprise at least one non-aqueous solvent, at least one electrolyte salt and, optionally, additives.

Non-aqueous solvents for electrolytes can be liquid or solid at room temperature and is preferably selected from among polymers, cyclic or acyclic ethers, cyclic and acyclic acetals and cyclic or acyclic organic carbonates.

Examples of suitable polymers are, in particular, polyalkylene glycols, preferably poly-C₁-C₄-alkylene glycols and in particular polyethylene glycols. Polyethylene glycols can here comprise up to 20 mol % of one or more C₁-C₄-alkylene glycols. Polyalkylene glycols are preferably polyalkylene glycols having two methyl or ethyl end caps.

The molecular weight M_(w) of suitable polyalkylene glycols and in particular suitable polyethylene glycols can be at least 400 g/mol.

The molecular weight M_(w) of suitable polyalkylene glycols and in particular suitable polyethylene glycols can be up to 5 000 000 g/mol, preferably up to 2 000 000 g/mol.

Examples of suitable acyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, with preference being given to 1,2-dimethoxyethane.

Examples of suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.

Examples of suitable acyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1,1-dimethoxyethane and 1,1-diethoxyethane.

Examples of suitable cyclic acetals are 1,3-dioxane and in particular 1,3-dioxolane.

Examples of suitable acyclic organic carbonates are dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.

Examples of suitable cyclic organic carbonates are compounds of the general formulae (III) and (IV)

where R¹, R² and R³ can be identical or different and are selected from among hydrogen and C₁-C₄-alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tertbutyl, with R² and R³ preferably not both being tert-butyl.

In particularly preferred embodiments, R¹ is methyl and R² and R³ are each hydrogen, or R¹, R² and R³ are each hydrogen.

Another preferred cyclic organic carbonate is vinylene carbonate, formula (V).

The solvent or solvents is/are preferably used in the water-free state, i.e. with a water content in the range from 1 ppm to 0.1% by weight, which can be determined, for example, by Karl-Fischer titration.

Electrolyte (C) further comprises at least one electrolyte salt. Suitable electrolyte salts are, in particular, lithium salts. Examples of suitable lithium salts are LiPF₆, LiBF₄, LiClO₄, LiAsF₆, LiCF₃SO₃, LiC(CnF_(2n+1)SO₂)₃, lithium imides such as LiN(CnF_(2n+1)SO₂)₂, where n is an integer in the range from 1 to 20, LiN(SO₂F)₂, Li₂SiF₆, LiSbF₆, LiAlCl₄ and salts of the general formula (CnF_(2n+1)SO₂)_(t)YLi, where m is defined as follows:

-   t=1, when Y is selected from among oxygen and sulfur, -   t=2, when Y is selected from among nitrogen and phosphorus, and -   t=3, when Y is selected from among carbon and silicon.

Preferred electrolyte salts are selected from among LiC(CF₃SO₂)₃, LiN(CF₃SO₂)₂, LiPF₆, LiBF₄, LiClO₄, with particular preference being given to LiPF₆ and LiN(CF₃SO₂)₂.

In an embodiment of the present invention, batteries according to the invention comprise one or more separators by means of which the electrodes are mechanically separated. Suitable separators are polymer films, in particular porous polymer films, which are unreactive toward metallic lithium. Particularly suitable materials for separators are polyolefins, in particular film-forming porous polyethylene and film-forming porous polypropylene.

Separators composed of polyolefin, in particular polyethylene or polypropylene, can have a porosity in the range from 35 to 45%. Suitable pore diameters are, for example, in the range from 30 to 500 nm.

In another embodiment of the present invention, separators can be selected from among PET nonwovens filled with inorganic particles. Such separators can have porosities in the range from 40 to 55%. Suitable pore diameters are, for example, in the range from 80 to 750 nm.

Batteries according to the invention further comprise a housing which can have any shape, for example cuboidal or the shape of a cylindrical disk or a cylindrical can. In one variant, a metal foil configured as a pouch is used as housing.

Batteries according to the invention display a good discharge behavior, for example at low temperatures (zero ° C. or below, for example down to −10° C. or even less), a very good discharge and cycling behavior, in particular at high temperatures (45° C. or higher, for example up to 60° C.) in particular with respect to the capacity loss, and a good safety behavior at high temperatures such as 60° C. or more. Preferably, also the cycle stability and the C-rate capacity behavior are improved, or they are at least identical although the Li content is lower.

Batteries according to the invention can comprise two or more electrochemical cells that combined with one another, for example can be connected in series or connected in parallel. Connection in series is preferred. In batteries according to the present invention, at least one of the electrochemical cells contains at least one cathode according to the invention. Preferably, in electrochemical cells according to the present invention, the majority of the electrochemical cells contains a cathode according to the present invention. Even more preferably, in batteries according to the present invention all the electrochemical cells contain cathodes according to the present invention.

The present invention further provides for the use of batteries according to the invention in appliances, in particular in mobile appliances. Examples of mobile appliances are vehicles, for example automobiles, bicycles, aircraft or water vehicles such as boats or ships. Other examples of mobile appliances are those which move manually, for example computers, especially laptops, telephones or electric hand tools, for example in the building sector, especially drills, battery-powered screwdrivers or battery-powered staplers.

The invention is further illustrated by working examples.

sccm: standard cubic centimeters per minute, cubic centimeters under standard conditions

I. Cathode Active Materials I.1. Preparation of a Precursor for Cathode Active Materials

A stirred tank reactor was filled with deionized water. The precipitation of mixed transition metal hydroxide precursor was started by simultaneous feed of an aqueous transition metal solution and an alkaline precipitation agent at a flow rate ratio of 1.9, and a total flow rate resulting in a residence time of 8 hours. The aqueous transition metal solution contained Ni, Co and Mn at a molar ratio of 6:2:2 as sulfates each and a total transition metal concentration of 1.65 mol/kg. The alkaline precipitation agent consisted of 25 wt. % sodium hydroxide solution and 25 wt. % ammonia solution in a weight ratio of 25. The pH value was kept at 11.9 by separate feed of an aqueous sodium hydroxide solution. After stabilization of particle size the resulting suspension was removed continuously from the stirred vessel. The mixed transition metal (TM) oxyhydroxide precursor was obtained by filtration of the resulting suspension, washing with distilled water, drying at 120° C. in air and sieving.

I.2. Manufacture of Cathode Active Materials

C-CAM.1 (Comparative): The mixed transition metal oxyhydroxide precursor obtained according to 1.1 was mixed with Al₂O₃ (average particle diameter 6 nm) and LiOH monohydrate to obtain a concentration of 0.3 mole-% Al relative to Ni+Co+Mn+Al and a Li/(TM+Al) molar ratio of 1.03. The mixture was heated to 885° C. and kept for 8 hours in a forced flow of oxygen to obtain the electrode active material C-CAM 1.

D50=9.5 μm determined using the technique of laser diffraction in a Mastersize 3000 instrument from Malvern Instruments. Al-content was determined by ICP analytics and corresponded to 820 ppm. Residual moisture at 250° C. was determined to be 300 ppm.

C-CAM.2 (comparative): A fluidized bed reactor with external heating jacket was charged with 100 g of C-CAM.1, and at an average pressure of 130 mbar, C-CAM.1 was fluidized. The fluidized bed reactor was heated to 180° C. and kept at 180° C. for 3 h. Trimethylaluminum (TMA) in the gaseous state was introduced into the fluidized bed reactor through a filter plater by opening a valve to a precursor reservoir that contained TMA in liquid form and that was kept at 50° C. The TMA was diluted with nitrogen as carrier gas. The gas flow of TMA and N₂ was 10 sccm. After a reaction period of 210 seconds non-reacted TMA was removed through the nitrogen stream, and the reactor was purged with nitrogen for 15 minutes with a flow of 30 sccm. Then, water in the gaseous state was introduced into the fluidized bed reactor by opening a valve to a reservoir that contained liquid water kept at 24° C., flow: 10 sccm. After a reaction period of 120 seconds non-reacted water was removed through a nitrogen stream, and the reactor was purged with nitrogen, 15 minutes at 30 sccm. The above sequence was repeated for three times. The reactor was cooled to 25° C. and the material was discharged. The resultant C-CAM.2 displayed the following properties: D50=10.6 μm determined using the technique of laser diffraction in a Mastersize 3000 instrument from Malvern Instruments. Al-content: 260 ppm, determined by inductively coupled plasma—emission spectroscopy (ICP-OES) with a PE-Optima 3300 RL instrument (typical detection limit of 3 ppm) via quantitation against a standard solution. Residual moisture at 250° C. was determined to be 120 ppm.

CAM.3 (Inventive): The manufacture of C-CAM.2 was repeated as above but without the fourth water treatment step. Instead, the fluidized bed reactor was connected to an ozone generator that produced an 8 wt. % O₃ in O₂ stream. Said O₃/O₂ mixture into the fluidized bed reactor for 30 minutes after opening the dosing valve, while N₂ was kept flowing at 10 sccm, step (c*.3).

After finishing the fourth circle, the reactor was purged with N₂ at 30 sccm for 1500 seconds.

Elemental analysis for aluminum content was carried out by ICP-OES with a PE-Optima 3300 RL instrument (typical detection limit of 3 ppm). After the coating, an Al uptake of 280 ppm was detected. Residual moisture at 250° C. was determined to be 110 ppm. CAM.3 was partially coated with acidic Al₂O₃.

CAM.4 (Inventive): The manufacture of C-CAM.2 was repeated as above but without the fourth water treatment step. Instead, the fluidized bed reactor was connected to an ozone generator that produced an 8 wt. % 03 in 02 stream. Said O₃/O₂ mixture into the fluidized bed reactor for 30 minutes after opening the dosing valve, while N₂ was kept flowing at 10 sccm (step c*.4).

After finishing the fourth circle, the reactor was purged with N₂ at 30 sccm for 1500 seconds. The sequence of TMA-treatment and step (C*.4) was repeated three times.

Elemental analysis for aluminum content was carried out by ICP-OES with a PE-Optima 3300 RL instrument (typical detection limit of 3 ppm) through quantitation against a standard solution. After the coating, an Al uptake of 280 ppm was detected. Residual moisture at 250° C. was determined to be 110 ppm. CAM.4 was partially coated with acidic Al₂O₃.

II Electrochemical Cells II.1. Manufacture of Electrodes for Electrochemical Testing

The positive electrodes for the electrochemical cycling experiments in single layer pouch cells were prepared by coating on aluminum foil (thickness=20 μm) using a continuous doctor knife coating system with subsequent drying (Mathis, KTF-S) a slurry containing 94 wt. % cathode active material (94 wt. %), 1 wt. % active carbon (Super C65 L purchased form Imerys), 2 wt. % graphite (SFG₆L from Imerys) and 3 wt. % polyvinylidene fluoride (PVdF) binders suspended in N-methyl-2-pyrrolidinone (NMP). Typically, all the slurries were prepared based on at least 30 g of cathode active material and the amount of NMP employed was such that the total solid content (CAM+SuperC65 L+SFG6L+PVdF) was ca. 65%. Before the cell assembly, the electrode tapes were dried in a hot-air chamber at 120° C. over a period of 16 hours and finally pressed using a roll calender.

II.2. Electrochemical Testing in Half-Cells

Electrochemical testing of cathode active materials (C-CAM.1, C-CAM.2, CAM.3, and CAM.4) were carried out in coin half cells (vs. Li metal as anode material to an upper cut-off voltage of 4.3V vs. Li/Li⁺, 1M LiPF₆ in EC:EMC wt % as electrolyte (EC=ethylene carbonate, EMC=ethyl methyl carbonate), GF/D glass fiber separator (Whatman), and CR2032 from Hohsen Corp.) to obtain a 1st cycle discharge capacity.

Inventive half-cells based upon CAM.3 or CAM.4 were superior over comparative half-cells based upon C-CAM.1 or C-CAM.2.

III Evaluation of Electrochemical Cells (Single Layer Pouch Cells)

Commercial graphite-coated tapes from Elexcel Corporation Ltd. were used as negative electrodes. The positive electrode comprising a cathode active material as described above, negative composite electrodes and a polypropylene separator (Celgard 2500 separator) were used to manufacture single layer pouch cells. Thereafter, all cells were filled with electrolyte (1M LiPF₆ in EC:DEC 3:7 wt % and VC 2 wt %, (DEC=diethyl carbonate, VC=vinylene carbonate)) in an argon-filled glove box having oxygen and water levels below 1.0 ppm and their electrochemical testing carried out in a Maccor 4000 battery-test system.

III.1. Formation at 25° C.

Pouch cells prepared comprising a cathode as described above and graphite anode were charged at a constant current of 0.1 C to a voltage of 4.25 V (CC charge). After degassing the cells, these are discharged at 0.1 C (3.0 V cut-off) (Cycle 1). Immediately after, the cells are charged at 25° C. at a constant current of 0.1 C to a voltage of 4.25 V (CC) and discharged at 0.1 C (3.0 V cut-off) (Cycle 2). Then, the cells are charged at a constant current of 0.5 C to a voltage of 4.25 V, charged at 4.25 V (CCCV) for either 60 minutes or until the current drops below 0.02 C and then the cells are discharged to a discharge voltage of 3 V at a constant current of 0.5 C (4 times, cycles 3 to 7). The cells were further cycled using the same charge conditions as in cycle 3 but using a discharge current of 10 (2 times, cycles 7 to 8), 2 C (2 times, cycles 9 to 10) and 3 C (2 times, cycles 11 to 12). Finally, the cells are charged and discharged 10 times following the same procedure as that used in cycle 3.

III.2. Evaluation of Cycling of Pouch Cell at 45° C. (Cycling) and 25° C. (Resistance Measurements) Using 4.25 V as Upper Cut-Off Voltage

Once the cells are formed, as described above, are charged at 25° C. a constant current of 0.2 C to a voltage of 4.25 V, charged at 4.25 V (CCCV) for either 60 minutes or until the current drops below 0.02 C and then the cells are discharged to a discharge voltage of 3 V at a constant current of 0.2 C. This procedure is repeated once and the discharge capacity is taken as the reference capacity for the next cycle. In this cycle, the cells are charge at a constant current of 0.2 C up to 75% of the reference capacity (75% state-of-charge=75% SoC) determined previously. Immediately after a 2.5 C current pulse was applied for 30 seconds (cell resistance measurement) in order to determine the cell resistance. The cells were then discharged at a constant current of 0.2 C to 50% and 25% SoC and cell resistance measurements were repeated for each of these SoC values. The cells are then further discharged to 3.0 V at a constant current of 0.2 C.

Following the above cell resistance measurements, the cells are transferred to a climate chamber kept at a constant temperature of 45° C. After a 12-hour equilibration time, the cells are charged at a constant current of 1 C to a voltage of 4.25 V, charged at 4.25 V (CCCV) for either 60 minutes or until the current drops below 0.02 C and then the cells are discharged to a discharge voltage of 3 V at a constant current of 1 C (100 times).

The complete sequence above described (resistance measurements at various SoC values at 25° C. and 1 C cycling at 45° C.) was repeated at least 5 times. The results after 500 cycles at 1 C and 45° C. from the various examples are presented in Table 2 and expressed as percentages relative to the values obtained at the beginning of the procedure.

Inventive pouch cells based upon CAM.3 or CAM.4 were superior over comparative pouch cells based upon C-CAM.1 or C-CAM.2. 

1. A process for making a partially coated electrode active material the process comprising: (a) treating an electrode active material with a metal alkoxide or metal halide or metal amide or alkyl metal compound, to obtain a material; (b) treating the material obtained in (b) with moisture; and, (c) repeating the treating (a) and the treating (b) twice to 4 times, wherein in a last sequence of the treating (a) and the treating (b), moisture is at least partially substituted by ozone, wherein the electrode active material subjected to the treating has a formula Li_(1+x)TM_(1−x)O₂,  wherein TM is a combination of Ni, Co, and, optionally, Mn, and, optionally, Al, Ti, Mo, W, and/or Zr in metallic form, and x is in a range of from zero to 0.2, wherein at least 60 mole-% of a transition metal of TM is Ni, and wherein the electrode active material has a residual moisture content in a range of from 50 to 1,000 ppm.
 2. The process of claim 1 wherein the TM is a combination of metals having a formula (I) (Ni_(a)co_(b)Mn_(c))_(1−d)M_(d)  (I), wherein a is in a range of from 0.6 to 0.95, b is in a range of from 0.025 to 0.2, c is in a range of from 0.025 to 0.2, d is in a range of from zero to 0.1, M is Al, and a+b+c=1.
 3. The process of claim 1, wherein the treating (a) is performed in a rotary kiln, a free fall mixer, a continuous vibrating bed, or a fluidized bed.
 4. The process of claim 1, wherein the alkyl metal compound is used in the treating (b) and is trimethylaluminum.
 5. The process of claim 1, wherein each flushing between the treating (a) and the treating (b) has a duration in a range of from 30 seconds to one hour.
 6. The process of claim 1, wherein the treating (a), the treating (b), and the repeating (c), are performed in a free-fall mixer.
 7. The process of claim 1, wherein the treating (a), the treating (b), and the repeating (c), are performed in a fluidized bed.
 8. The process of claim 1, wherein the TM is Ni_(0.6)Co_(0.2)Mn_(0.2).
 9. The process of claim 1, wherein, in the last sequence of the treating (a) and the treating (b), moisture is fully replaced by ozone.
 10. A particulate electrode active material, having a formula Li_(1+x)TM_(1−x)O₂, wherein TM is a combination of Ni, Co, and, optionally, Mn, and, optionally, Al, Ti, Mo, W, and/or Zr, and x is in a range of from zero to 0.2, wherein at least 60 mole-% of a transition metal of TM is Ni, wherein an outer surface of particles of the particulate electrode active material is non-homogeneously coated with acidic aluminum oxyhydroxide or acidic alumina.
 11. The material of claim 10 wherein the TM is Ni_(0.6)Co_(0.2)Mn_(0.2), Ni_(0.7)CO_(0.2)Mn_(0.1), and Ni_(0.8)Co_(0.1)Mn_(0.1).
 12. A lithium ion battery, comprising the material of claim
 10. 13. The process of claim 1, wherein the alkyl metal compound is used in the treating (b) and is triethylaluminum.
 14. The process of claim 1, wherein the TM is Ni_(0.7)Co_(0.2)Mn_(0.1).
 15. The process of claim 1, wherein the TM is Ni_(0.8)CO_(0.1)Mn_(0.1).
 16. The process of claim 1, wherein the TM is Ni_(0.85)Co_(0.1)Mn_(0.05).
 17. The process of claim 1, wherein the TM of the electrode active material comprises the Mn.
 18. The process of claim 1, wherein the TM of the electrode active material comprises the Al.
 19. The process of claim 1, wherein the TM of the electrode active material comprises the Ti. 